CN1942830A - Polymerized toner with high chargeability and good charge stability and preparatiion method thereof - Google Patents

Polymerized toner with high chargeability and good charge stability and preparatiion method thereof Download PDF

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Publication number
CN1942830A
CN1942830A CNA2006800000414A CN200680000041A CN1942830A CN 1942830 A CN1942830 A CN 1942830A CN A2006800000414 A CNA2006800000414 A CN A2006800000414A CN 200680000041 A CN200680000041 A CN 200680000041A CN 1942830 A CN1942830 A CN 1942830A
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China
Prior art keywords
monomer
pigment
toner
polymerization
styrene
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CNA2006800000414A
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CN100514200C (en
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李雄基
李昶淳
尹泰熙
郑宇哲
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LG Corp
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LG Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08706—Polymers of alkenyl-aromatic compounds
    • G03G9/08708—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08706—Polymers of alkenyl-aromatic compounds
    • G03G9/08708—Copolymers of styrene
    • G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08726—Polymers of unsaturated acids or derivatives thereof
    • G03G9/08728—Polymers of esters
    • G—PHYSICS
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    • G03G9/08737—Polymers derived from conjugated dienes
    • G—PHYSICS
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    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08788—Block polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/00—Developers
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    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G—PHYSICS
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    • G—PHYSICS
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    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds

Abstract

The present invention relates to a polymerized toner with high chargeability and good charge-stability, and a method of preparing the polymerized toner. In particular, the present invention relates to a polymerized toner containing pigments, pigment stabilizers, charge control agents and binder resin monomers, and a method to prepare the polymerized toner by suspension polymerization of pigments, pigment stabilizers, charge control agents and binder resin monomers, wherein the pigment stabilizer is a styrene-butadiene-styrene block copolymer having the weight-average molecular weight of 2,000 to 200,000, and the charge control agent is a copolymer with sulfonate group having the weight-average molecular weight of 2,000 to 200,000.

Description

Has polymerization toner of high chargeability and good charge stability and preparation method thereof
Related application
The application requires in the right of priority of the Korean Patent Application No. 10-2005-0019027 of submission on March 8th, 2005, and for the various purposes in this comprehensive elaboration, this application is incorporated this paper into way of reference.
Technical field
The present invention relates to a kind of polymerization toner with high chargeability and good charge stability, and the method for preparing this polymerization toner.Specifically, the present invention relates to a kind of polymerization toner that comprises pigment, pigment stabiliser, charge control agent and binder resin monomer, and the method for preparing this polymerization toner by the suspension polymerization of pigment, pigment stabiliser, charge control agent and binder resin monomer, wherein pigment stabiliser is that weight-average molecular weight is 2,000～200,000 styrene-butadiene-styrene block copolymer, and charge control agent is that weight-average molecular weight is 2,000～200,000 the multipolymer that contains sulphonate-base.
In the present invention,, improved the charge characteristic of this polymerization toner, thereby obtained the high chargeability of this toner and good charge stability by the combination of pigment stabiliser and charge control agent.
Background technology
In general, toner is used for electrophotography and electrostatic printer, duplicating machine etc., is meant the pigment that forms image on the material of wanting the transfer printing epigraph gradually.Recently, because become file with computing mechanism usually, so have very big demand for device as the rapid formation image of printer.Therefore, the consumption of toner also constantly increases.
Usually, can be used for toner by making colorant as carbon black or other adjuvant be dispersed in the binder resin and making the toner that particle prepares.The method for preparing toner mainly is divided into comminuting method and polymerization.In comminuting method, toner prepares by following steps: make synthetic resin and colorant, optional other adjuvant fusion and mixing, pulverize then, thereby obtain the toner of desired particle size.Yet, have the Particle Distribution of broad by the toner particle of well-known fusion-mixing method preparation, and be the particulate of sharp edge-shaped for out-of-shape.Therefore, this toner has relatively poor chargeability and flowing property (flowing capacity).
In order to address this is that, the polymerization of spherical toner has been proposed.Polymerization is divided into emulsion polymerization and suspension polymerization.Emulsion polymerization is complicated, thereby the toner that makes has relatively poor quality repeatability.Therefore, suspension polymerization is better than emulsion polymerization.In suspension polymerization, by making monomer, colorant, polymerization initiator and preparing monomer composition as optional other adjuvant uniform dissolution or the dispersion of crosslinking chemical and charge control agent; By using stirrer to disperse to comprise the aqueous dispersant of dispersions-stabilizing agent (dispersing-stabilizing agent), with the formation droplet; The temperature that raises is then carried out suspension polymerization, thereby makes the toner particle with required size.
U.S. Patent number 4,883,735 have disclosed, and for the relatively poor compatibility of improving compound (complex) charge control agent that comprises metal and lower stability, use and contain the multipolymer of sulphonate-base as charge control agent.In addition, JP H02-167565 A1, JP 2000-056518 A1, JP H03-243954 A, JP S63-184762 A1 and JP H03-161761 have also disclosed a kind of toner that comprises as the polymkeric substance that contains sulphonate-base of charge control agent.
Yet disclosed in above-mentioned document, if this polymkeric substance is used as charge control agent, this pigment accumulates in polymerization process on the surface of toner owing to its surfactivity, thereby makes the chargeability variation of toner.In addition because the polymer charge controlling agent is owing to the bigger surface area of pigment is attracted on the surface of pigment, so the amount of the charge control agent of working control electric charge reduce to some extent, thereby reduced chargeability and charge stability.
Summary of the invention
In order to solve the aforementioned problems in the prior, for the high chargeability of acquisition toner and good charge stability, an object of the present invention is to provide a kind of polymerization toner that comprises pigment, pigment stabiliser, charge control agent and binder resin monomer.
Another object of the present invention provides a kind of method for preparing this polymerization toner, and this method comprises makes pigment, pigment stabiliser, charge control agent and binder resin monomer step of polymerization.
The inventor finds, when preparing toner by suspension polymerization, is adsorbed on chargeability and the charge stability that has reduced toner on the surface of pigments owing to pigment accumulates on the toner surface with charge control agent.In order to address this problem, and for the reduction of the control electric charge ability that effectively stops pigment to accumulate on the toner surface and cause by the absorption of charge control agent, the inventor has made the present invention, and the present invention contains sulphonate-base by use multipolymer is finished as pigment stabiliser as the charge control agent and the segmented copolymer that can effectively be adsorbed on the surface of pigments.Therefore, obtained uniform chargeding performance (electrification), and improved chargeding performance.
In an embodiment of the invention, the present invention relates to a kind of polymerization toner that comprises pigment, pigment stabiliser, charge control agent and binder resin, wherein pigment stabiliser is that weight-average molecular weight is 2,000～200,000, styrene-content is the styrene-butadiene-styrene block copolymer of 10～90wt%, and charge control agent is that weight-average molecular weight is 2,000～200,000 the multipolymer that contains sulphonate-base.
In another embodiment, the present invention relates to a kind of preparation method of polymerization toner, this method comprises the step that makes pigment, pigment stabiliser, charge control agent and binder resin monomer carry out suspension polymerization in aqueous dispersant.
In another embodiment, the present invention relates to a kind of preparation method of polymerization toner, this method comprises that making pigment, weight-average molecular weight is 2,000～200, the pigment stabiliser of 000 styrene-butadiene-styrene block copolymer, weight-average molecular weight are 2, the charge control agent of 000～200,000 the multipolymer that contains sulphonate-base and binder resin monomer are carried out the step of suspension polymerization in comprising the aqueous dispersion of spreading agent.
Embodiment
When the reference following detailed is understood when of the present invention better, the present invention is more fully understood and many advantages of bringing will become apparent.
The monomer (hereinafter, being called " binder resin monomer ") that is used to prepare binder resin is any monomer that can be used for preparing toner by polymerization.The example of this monomer is the monomer of styrene-based, based on the monomer of acrylate, based on the monomer of methacrylate, based on monomer of diene and composition thereof etc.In addition, this monomer can be chosen wantonly to be selected from and comprise based on the monomer of acidic olefin with based on the mode of at least a potpourri in the group of the monomer of alkaline alkene and using.
In an embodiment of the invention, described binder resin monomer comprises: (a) monomer of the styrene-based of 30～95 weight portions; (b) one or more of 5～70 weight portions be selected from the monomer that comprises based on acrylate, based on the monomer of methacrylate with based on the monomer in the group of the monomer of diene.Perhaps, based on the total amount that comprises (a) and monomer composition (b) of 100 weight portions, this monomer composition further comprises: (c) 0.1～30 weight portion at least a is selected from and comprises based on the monomer of acidic olefin with based on the monomer in the group of the monomer of alkaline alkene.
The monomer of described styrene-based is styrene, monochloro styrene, methyl styrene, dimethyl styrene etc.Based on the total amount that comprises (a) and monomer composition (b) of 100 weight portions, the consumption of the monomer of this styrene-based can be 30～95 weight portions.
Described monomer based on acrylate comprises methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecylacrylate, 2-ethylhexyl acrylate etc.Described monomer based on methacrylate comprises methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, isobutyl methacrylate, lauryl methacrylate, methacrylic acid 2-ethylhexyl etc.Described monomer based on diene is butadiene and isoprene etc.Based on 100 weight portions comprise (a) and monomer composition (b), at least aly be selected from the monomer that comprises based on acrylate, can be 5～70 weight portions based on the monomer of methacrylate with based on the consumption of the monomer in the group of the monomer of diene.
Described monomer based on acidic olefin is the α that contains carboxyl, β-vinyl compound (α, β-ethylene compound), and described monomer based on alkaline alkene be methacrylic acid aliphatic alcohol ester, Methacrylamide, vinylamine, diallylamine or its ammonium salt that contains amido or quaternary ammonium group.Based on 100 weight portions comprise (a) and monomer composition (b), at least aly be selected from based on the monomer of acidic olefin and be 0.1～30 weight portion based on the consumption of the monomer in the monomer of alkaline alkene.
In yet another embodiment of the present invention, comprise monomer (a) and (b) and (c) monomer composition, at least a polymkeric substance that comprises based in the group of the polymkeric substance of the polymkeric substance of polyester and styrene-based-acrylate that is selected from that described monomer composition is optional further to comprise 0.01～10 weight portion based on 100 weight portions.
Described pigment stabiliser is for having the styrene-butadiene-styrene block copolymer of 2,000～200,000 weight-average molecular weight.Preferably, in styrene-butadiene-styrene block copolymer, the weight ratio of butadiene and styrene-content is 10-90: 90-10.If cinnamic content surpasses 90wt%, then since with the high-compatibility of binder resin, butadiene block is too short so that can not play the effect of pigment stabiliser.If cinnamic content is less than 10wt%, its abundant stable pigments then, but because the length of styrene block is shorter, it can not control the interaction of pigment and pigment.In addition, if the molecular weight of s-B-S block less than 2,000, then since with the high-compatibility of binder resin, it can not play the effect of pigment stabiliser.If the molecular weight of s-B-S block is greater than 200,000, then the too high viscosity of monomer composition has reduced dispersion stabilization and polymerization stability, thereby makes broad particle distribution.In the present invention, based on the total amount of 100 parts by weight of adhesive with resin monomer, the consumption of this pigment stabiliser can be 0.1～20 weight portion.
Described charge control agent can be the multipolymer that contains sulphonate-base, be preferably and have 2, the multipolymer of 000～200,000 weight-average molecular weight, more preferably acid number is that 1～40mg KOH/g, glass transition temperature are 30 ℃～120 ℃ the multipolymer that contains sulphonate-base.If acid number is less than 1, then this multipolymer can not play the effect of charge control agent.If acid number is greater than 40, then this multipolymer influences the interfacial characteristics of described monomer composition, thereby reduces polymerization stability.In addition, if glass transition temperature is lower than 30 ℃, the lower glass transition temperature that then is exposed to the charge control agent of toner surface can cause friction and the fusion (melting) between the toner, thereby causes obstruction when using this toner to print.If glass transition temperature is higher than 120 ℃, then this multipolymer makes toner surface too hard, thereby has reduced the coating characteristic and caused the photographic fixing problem.In addition, if weight-average molecular weight is lower than 2,000, then, reduces the high-compatibility with binder resin, so this multipolymer can not play the effect of charge control agent owing to causing the concentration of this multipolymer on toner surface.If weight-average molecular weight is higher than 200,000, then the high viscosity of described monomer composition has adverse influence to polymerization stability and size-grade distribution.
The example of described charge control agent comprises the multipolymer of one or more multipolymers that are selected from the styrene-based-acrylate that contains sulphonate-base and the multipolymer of the styrene-based-methacrylate that contains sulphonate-base, but is not limited thereto.In the present invention, based on the total amount of 100 parts by weight of adhesive with resin monomer, the consumption of this charge control agent can be 0.1～20 weight portion.
Described pigment can be any pigment that is generally used for polymerization toner, for example metal powder class pigment, metal oxide-type pigments, carbon class pigment, sulfide-based pigment, chromic salts class pigment, ferrocyanide class pigment, azo class pigment, acid stain class pigment, alkali stain class pigment, mordant dyeing colorant class pigment, phthalocyanine pigment, quinacridine ketone pigment, dioxane class pigment and composition thereof.In the present invention, based on the total amount of 100 parts by weight of adhesive with resin monomer, the consumption of this pigment is 1～20 weight portion.
According to the present invention, except pigment, pigment stabiliser, charge control agent and binder resin monomer, described toner can comprise further that one or more are selected from the adjuvant in the group that comprises wax, chain-transferring agent, reaction initiator, crosslinking chemical, lubricant (for example, oleic acid and stearic acid etc.) and coupling agent.
Described wax is at least a wax that is selected from the group that comprises wax as described below, promptly comprises: as the turpentole wax of paraffin, microcrystalline wax and ceresine; Natural wax as Brazil wax; Be selected from the synthetic wax in the group of the wax that comprises based on polyester, Tissuemat E, polypropylene wax and composition thereof.In the present invention, based on the total amount of 100 parts by weight of adhesive with resin monomer, the consumption of this wax is 0.1～30 weight portion.
Described chain-transferring agent is to be selected from least a in the group that comprises uncle's lauryl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, phenixin and carbon tetrabromide.Based on the total amount of 100 parts by weight of adhesive with resin monomer, the consumption of this chain-transferring agent can be 0.001～8.000 weight portion.
Described reaction initiator is oil-soluble initiator and water soluble starter.More particularly, this reaction initiator is the azo-initiator as azoisobutyronitrile and azo two valeronitriles; Organic peroxide as benzoyl peroxide and lauroyl peroxide; Normally used water soluble starter as potassium persulfate and ammonium peroxydisulfate etc.Based on the bonding agent of the 100 weight portions total amount with resin monomer, the consumption of this initiating agent can be 0.01～5.00 weight portion, more preferably 0.1～2.0 weight portion.
Described crosslinking chemical comprises divinylbenzene, dimethacrylate second diester, ethylene glycol, dimethacrylate, diethylene glycol, diacrylate, diacrylate-1, the inferior own ester of 6-, allyl methacrylate, 1,1,1-trimethylolpropane, triacrylate, triallylamine, tetraene propoxyl group ethane (tetraallyloxyethane) etc.Based on the total amount of 100 parts by weight of adhesive with resin monomer, the consumption of this crosslinking chemical can be 0.001～10 weight portion.
In embodiments of the present invention, described polymerization toner can be made into have core pattern, the structure of polymerization forms shell on the core particulate core-shell, core-shell-shell mould etc.Another embodiment of the invention provides a kind of core-shell polymerization toner, this polymerization toner comprises core that contains pigment, pigment stabiliser, charge control agent and the monomer that is used to form shell, and by monomer, crosslinking chemical and the polymerization initiator polymerization that is used in the preparation shell shell is formed on core.This shell can form one or more layers.When polymerization toner prepares with the form of core-shell, then can stop the reduction that exposes the chargeability that causes from the teeth outwards owing to pigment, and the storage life that can prolong toner.In addition, become the situation of one deck for hull shape, wherein charge control agent is positioned at internal layer and causes the increase of hydroscopicity (hygroscopicity) and chargeability, comparatively speaking, become two layers situation for hull shape, for prolonging storage life is favourable, and this is because charge control agent can be positioned at second (outward) layer, thereby has improved chargeability and reduced hydroscopicity.
The kind and the amount that are used to form the monomer of shell can be the aforesaid binder resin monomer that is used to form core.The binder resin monomer that is used to form shell can be identical or different with the monomer that is used for core.The amount that is used to form the monomer of shell can be determined according to the number of plies of shell.Preferably, based on the total amount of the binder resin monomer that is used to form core of 100 weight portions, the content that is used to form the binder resin monomer of shell can be 0.01～50 weight portion.Compare with the core pattern toner, owing to the core-shell toner can not reunited under high humility and temperature, so it has better long-time stability.Core-shell-shell mould comprise have highly charged characteristic (charging property) the ground floor shell and the toner that can obtain to have higher charged and long-time stability is provided under the situation of second layer shell of long-time stability.
In the present invention, the granularity of described toner can be 2～20 μ m, is preferably 3～15 μ m, more preferably 5～8 μ m.
According to the present invention, prepare that the method for polymerization toner is optional to comprise the step that prepare core, or on core, prepare the step of shell.In addition, can comprise i by being selected from) step of removing spreading agent, ii) wash, filter and dry step, and at least one step in the group of the step that iii) applies with silica surface and carry out post-processing step.In preferred implementation of the present invention, the method for polymerization toner is described in detail.
(1) preparation of polymerization toner
By being dissolved in, spreading agent prepares aqueous dispersion in the aqueous solution.Based on the total amount of 100 parts by weight of adhesive with resin monomer, this spreading agent can be at least a spreading agent that is selected from the group that comprises inorganic dispersant, water-soluble organic polymer spreading agent and anionic surface active agent of 0.1～20 weight portion.
The example of inorganic dispersant comprises insoluble calcium phosphate, insoluble magnesium salts, water wettability silicon dioxide, hydrophobic silica, cataloid etc.The example of water-soluble organic polymer is the non-ionic polymers as polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenol ether, sorbitan fatty acid esters, polyoxyalkylene fatty acid ester, fatty glyceride, polyvinyl alcohol (PVA), alkylcellulose, polyvinylpyrrolidone; With as ionomer spreading agent of polyacrylamide, polyvinylamine, tygon amine n-oxide (polyvinylamine N-oxide), tygon ammonium (polyvinylammonium), poly-diakyl allyl-ammonium (polydialkylallyl ammonium), polyacrylic acid, polystyrolsulfon acid, polyacrylate, poly styrene sulfonate (polystyrene sulfonate), polyacrylate and amino Arrcostab etc. etc.Described anionic surface active agent is soap, alkyl sulfonate esters, alkyl aryl sulfonic acid ester, dialkyl sulfosuccinate, alkylphosphonate etc.
According to the embodiment of the present invention, will comprise that 100 parts by weight of adhesive are dissolved in 1～60 weight portion of the composition of the polymer charge controlling agent of the pigment stabiliser of the pigment of resin monomer, 1～20 weight portion, 0.1～20 weight portion and 0.1～20 weight portion in the aqueous dispersion of 100 weight portions with the preparation mixture solution.Then, by utilize this mixed solution of shearing force punching press to prepare the core of polymerization toner with homogenizer.
Perhaps, at least a monomer that is selected from the group of the polymkeric substance that comprises polyester and styrene-based-acryloyl group can be added in this monomer composition with the amount of 0.01～10 weight portion.
In embodiments of the present invention, based on the total monomer amount of 100 weight portions, at least a adjuvant that is selected from the group of reaction initiator of the chain-transferring agent of the wax that comprises 0.1～30 weight portion, 0.001～10 parts by weight of cross-linking agent, 0.001～8 weight portion and 0.01～5 weight portion can be added in this monomer composition.
(2) on core, prepare shell
Perhaps, can form shell by formation shell composition and by the shell composition is coated on the core particulate, thereby make the core-shell toner, its mesochite composition carries out suspension polymerization by the binder resin monomer that is used in the formation shell and makes.This shell composition can comprise binder resin monomer, crosslinking chemical, initiating agent and the optional charge control agent that is used to form shell.The monomer that is used to form shell can be any monomer that is used to prepare toner core, and can be identical or different with the binder resin monomer that is used for toner core.
Based on the total amount of the monomer that is used for toner core of 100 weight portions, the amount that is used to form the monomer of shell can be 0.01～50 weight portion.The shell that forms on the core of toner can be made up of one deck at least, preferably forms by two layers.
(3) aftertreatment
To the resulting solution usable acid that contains polymerization toner or core-shell polymerization toner or alkali treatment removing spreading agent, the step of washing repeatedly and filtering, thus isolate toner.At room temperature, can be in vacuum drying oven dry isolated toner, obtain toner powder.In embodiments of the present invention, if cataloid is used as aqueous dispersion, then available 0.05～0.2N NaOH aqueous solution is handled and is removed silicon dioxide from toner surface.In order to prepare final product of toner, can further handle the toner of drying by the surface treatment of silicon dioxide.
The imaging device that polymerization toner of the present invention is suitable for can comprise photosensitive drums (photoconductive drum), be used to make the device of photosensitive drum surface charging, be used on photosensitive drum surface, forming electrostatic latent image device, be used to hold toner device, be used to the device that makes image development and form toner image and be used for toner image is transferred to the device of transferring member.
Polymerization toner of the present invention can be applicable to the method according to formation image of the present invention, and this method comprises by making toner stick on the electrostatic latent image on the photosensitive drums and forming the step of visual picture to transferring member transfer printing visual picture.
With reference to the following examples, the present invention further is described in detail.Yet these embodiment should not be construed as by any way and limit the scope of the invention.
Embodiment 1
1-1: the preparation of toner suspension
400g distilled water and 10g are dissolved in the 500ml reactor as the cataloid of spreading agent, and be heated to 70 ℃ temperature of reaction, thus the preparation aqueous dispersion.
Will be as 160g styrene, 36g butyl acrylate and the 4g acrylic acid of monomer, 4g mixes as the n-dodecyl mercaptan of chain-transferring agent as the allyl methacrylate of crosslinking chemical and 0.02g.Then; the charge control agent and the 3.5g that 2.3g are contained the styrene-based-acryloyl group of sulphonate-base fully are dissolved in the potpourri of above-mentioned acquisition as the symmetrical segmented copolymer of the s-B-S of pigment stabiliser; wherein the weight-average molecular weight of this charge control agent is 10; 000g/mol; it is 21mgKOH/g with acid number that glass transition temperature is 59 ℃; cinnamic content in this pigment stabiliser is 30wt%, and weight-average molecular weight is 70,000g/mol.To wherein adding the 10g carbon black, stirred 2 hours with 2000rpm with ball bowl mill (bead mill).Then, remove ball, thus the potpourri of preparation 105g monomer and pigment.The water-bath that the potpourri of the monomer of above-mentioned acquisition and pigment is put into 70 ℃ is heated.Then, add 5g paraffin and stirring 20 minutes so that it fully dissolves.In the potpourri of above-mentioned acquisition, add 2g as the azoisobutyronitrile of initiating agent and stirred 5 minutes.
The above-mentioned reaction mixture that makes is added in the aqueous dispersion, and with 10,000rpm stirred 20 minutes with homogenizer, so that this reaction is carried out continuously, stirred 15 hours with 600rpm with conventional stirrer then, thus the preparation toner suspension.
1-2: aftertreatment
In the toner suspension of preparation, add the NaOH aqueous solution, and with the concentration adjustment of NaOH to 0.1N, thereby remove silicon dioxide as spreading agent from the surface of toner particle.Remove aggregate with No. 150 sieves, drying is also weighed.
The resulting product of removing silicon dioxide is repeated the operation of centrifuging-decant supernatant-disperse again, thereby remove spreading agent and secondary product.Finally, filter resulting product removing moisture, the toner mud cake that makes was put into vacuum drying oven and vacuum drying at room temperature 48 hours, thus the preparation toner powder.
Use Multisizer TMThe granularity of the toner powder that the measurement of Coulter measuring appliance makes, and observe the shape of this particulate with SEM.Based on the theoretical amount of toner, the amount of aggregate is 1.2wt%.The volume mean diameter of the toner particle that obtains is 7.2 μ m, and diameter Distribution (diameterdistribution) is 1.8 μ m.
Surface-treated silicon dioxide RY200S as external additive (external additive) adds in the toner powder that makes with 2 weight portions, and mixes 3 minutes with 4000rpm in stirring machine, thereby prepares surface-treated finished product.(Hewlett-Packard) prints test to the finished product that makes with the HP4600 printer, and measures image density (ID) with Macbeth (model RD918).It the results are shown in the following table 1.
Embodiment 2～5: the toner of adjusting pigment stabiliser
Except as the block of the styrene-butadiene-styrene block copolymer of pigment stabiliser than the change of (styrene wt%) is as shown in following table 1, carry out polyreaction and remove silicon dioxide from the toner particle surface with method substantially the same manner as Example 1 as spreading agent.Remove aggregate with No. 150 sieves, drying is also measured its amount.Based on the amount of toner, the amount of aggregate is about 1～2wt%.
By method substantially the same manner as Example 1 by resulting preparation of product toner mud cake, toner powder and the finished product of removing silicon dioxide.The size of the toner particle that makes is in the scope of 6.8 μ m～7.5 μ m.The toner that makes is printed test, and measure its image density.It the results are shown in the following table 1.
Embodiment 6～10: the toner of adjusting charge control agent
To have block be 70 than (styrene wt%) as 30wt%, weight-average molecular weight except using, the styrene-butadiene-styrene block copolymer of 000g/mol is as pigment stabiliser, the change of molecular weight, acid number and glass temperature that contains the charge control agent of sulphonate-base as shown in following table 1 outside, carry out polyreaction and remove silicon dioxide from the toner particle surface with method substantially the same manner as Example 1 as spreading agent.Sieve with numbering 150 is removed aggregate, and drying is also measured its amount.Based on the amount of toner, the amount of aggregate is about 1～2wt%.
By method substantially the same manner as Example 1 by resulting preparation of product toner mud cake, toner powder and the finished product of removing silicon dioxide.The size of the toner particle that makes is in the scope of 6.8 μ m～7.5 μ m.The toner that makes is printed test, and measure its image density.It the results are shown in the following table 1.
Comparative example 1
Do not use pigment stabiliser to prepare toner
Except under as the non-existent situation of the styrene-butadiene-styrene block copolymer of pigment stabiliser, carrying out the polyreaction, carry out polyreaction and remove silicon dioxide from the toner particle surface as spreading agent with method substantially the same manner as Example 1.Remove aggregate with No. 150 sieves, drying is also measured its amount.Based on the amount of toner, the amount of aggregate is about 1.5wt%.
By method substantially the same manner as Example 1 by resulting preparation of product toner mud cake, toner powder and the finished product of removing silicon dioxide.The toner that makes is printed test, and measure its image density.It the results are shown in the following table 1.
Comparative example 2
Use styrene-content to prepare toner as the styrene-butadiene-styrene block copolymer of 95wt%
To have block be 120 than (styrene wt%) as 95wt%, weight-average molecular weight except using, the styrene-butadiene-styrene block copolymer of 000g/mol is as outside the pigment stabiliser, carries out polyreaction and removes silicon dioxide as spreading agent from the toner particle surface with method substantially the same manner as Example 1.Remove aggregate with No. 150 sieves, drying is also measured its amount.Based on the amount of toner, the amount of aggregate is about 35wt%.
By method substantially the same manner as Example 1 by resulting preparation of product toner mud cake, toner powder and the finished product of removing silicon dioxide.The toner that makes is printed test, and measure it as density.It the results are shown in the following table 1.
Comparative example 3
Use styrene-content to prepare toner as the styrene-butadiene-styrene block copolymer of 5wt%
To have block be 56 than (styrene wt%) as 5wt%, weight-average molecular weight except using, the styrene-butadiene-styrene block copolymer of 000g/mol is as outside the pigment stabiliser, carries out polyreaction and removes silicon dioxide as spreading agent from the toner particle surface with method substantially the same manner as Example 1.Remove aggregate with No. 150 sieves, drying is also measured its amount.Based on the amount of toner, the amount of aggregate is about 2.0wt%.
By method substantially the same manner as Example 1 by resulting preparation of product toner mud cake, toner powder and the finished product of removing silicon dioxide.The toner that makes is printed test, and measure its image density.It the results are shown in the following table 1.
Table 1
Sample number into spectrum S-B-S Charge control agent ID
Cinnamic content (wt%) Molecular weight (g/mol) Content (wt%) Molecular weight (g/mol) Acid number (mgKOH/ g) Tg (℃) Content (wt%) 1 page 200 pages
Embodiment 1 30 70,000 1.5 10,000 21 59 1.0 1.45 1.42
Embodiment 2 10 75,000 1.5 10,000 21 59 1.0 1.42 1.39
Embodiment 3 20 72,000 1.5 10,000 21 59 1.0 1.43 1.40
Embodiment 4 50 67,000 1.5 10,000 21 59 1.0 1.39 1.33
Embodiment 5 70 100,000 1.5 10,000 21 59 1.0 1.38 1.32
Embodiment 6 30 70,000 1.5 12,000 5 57 1.0 1.30 1.27
Embodiment 7 30 70,000 1.5 11,500 36 67 1.0 1.46 1.42
Embodiment 8 30 70,000 1.5 22,000 11 62 1.0 1.35 1.33
Embodiment 9 30 70,000 1.5 124,000 20 81 1.0 1.46 1.44
Embodiment 10 30 70,000 1.5 4,800 15 57 1.0 1.32 1.30
Comparative example 1 - - 0 10,000 21 59 1.0 1.20 0.98
Comparative example 2 95 120,000 1.5 10,000 21 59 1.0 1.35 1.23
Comparative example 3 5 56,000 1.5 10,000 21 59 1.0 1.37 1.21
As shown in table 1, in the comparative example 1 that does not use as the styrene-butadiene-styrene block copolymer of pigment stabiliser, can not keep the developing property that image density significantly descends in the time of 200 pages to such an extent as to show.In addition, by comparative example 2 as can be known, cinnamic content in the s-B-S multipolymer be 95% or more situation under, there is following several problem: because the length of butadiene block is shorter, make surface of pigments insufficient, thereby reduced charge stability the absorption of this multipolymer; And the multipolymer that is not adsorbed on the surface of pigments can influence the interface performance of this toner, thereby reduces polymerization stability and produce a large amount of aggregates.In addition, by comparative example 3 as can be known, cinnamic content in the s-B-S multipolymer be 5% or situation still less under, although polymerization stability is good, but exist owing to the short interactional problem that does not have fully to stop between the pigment of the length of styrene block, thereby cause the pigment reunion, cause charge characteristic to worsen along with the time.
From foregoing as can be known, in embodiments of the invention 1～10, in order to prepare the toner with high chargeability and good charge stability, the block that can suitably adjust the s-B-S multipolymer compares and/or contains the performance of the charge control agent of sulphonate-base.
As mentioned above, compare with the polymerization toner of routine, the present invention is by using styrene-butadiene-styrene block copolymer as pigment stabiliser, and the charge control agent that contains sulphonate-base by suitable adjustment, thereby stoped the reduction of on toner surface, assembling the chargeability that causes owing to pigment, thereby guaranteed high chargeability and good charge stability, therefore the invention provides a kind of polymerization toner of practicality with high chargeability and good charge stability.

Claims (21)

1, a kind of polymerization toner, it comprises pigment, pigment stabiliser, charge control agent and binder resin monomer,
Wherein said pigment stabiliser is that weight-average molecular weight is 2,000～200,000, styrene-content is the styrene-butadiene-styrene block copolymer of 10～90wt%, and described charge control agent is that weight-average molecular weight is 2,000～200,000 the multipolymer that contains sulphonate-base.
2, polymerization toner according to claim 1, wherein, described charge control agent is that acid number is that 1～40mg KOH/g, glass transition temperature are 30 ℃～120 ℃ the multipolymer that contains sulphonate-base.
3, polymerization toner according to claim 1; wherein, described charge control agent is to be selected from the multipolymer that comprises the styrene-based-acryloyl group that contains sulphonate-base and to contain one or more multipolymers in the group of multipolymer of styrene-based-methacryl of sulphonate-base.
4, polymerization toner according to claim 1, wherein, based on the total amount of 100 parts by weight of adhesive with resin monomer, the amount of described pigment stabiliser is 0.1～20 weight portion, and the amount of described charge control agent is 0.1～20 weight portion.
5, polymerization toner according to claim 1, wherein, described binder resin monomer be selected from the monomer that comprises styrene-based, based on the monomer of acrylate, based on the monomer of methacrylate with based on one or more monomers in the group of the monomer of diene.
6, polymerization toner according to claim 5, wherein, described binder resin monomer comprise (a) 30～95 weight portions styrene-based monomer and (b) 5～70 weight portions be selected from the monomer that comprises based on acrylate, based on the monomer of methacrylate with based on one or more monomers in the group of the monomer of diene.
7, polymerization toner according to claim 6, wherein, based on the monomer (a) and the total amount (b) of 100 weight portions, described binder resin monomer further comprise (c) 0.1～30 weight portion based on the monomer of acidic olefin with based on one or more monomers in the monomer of alkaline alkene.
8, polymerization toner according to claim 1, wherein, described pigment is one or more pigment that are selected from the group that comprises metal powder class pigment, metal oxide-type pigments, carbon class pigment, sulfide-based pigment, chromic salts class pigment, ferrocyanide class pigment, azo class pigment, acid stain class pigment, alkali stain class pigment, mordant dyeing colorant class pigment, phthalocyanine pigment, quinacridine ketone pigment and dioxane class pigment.
9, polymerization toner according to claim 1, wherein, based on the total amount of 100 parts by weight of adhesive with resin monomer, the amount of described pigment is 1～20 weight portion, the amount of described pigment stabiliser is 0.1～20 weight portion, and the amount of described charge control agent is 0.1～20 weight portion.
10, polymerization toner according to claim 1, wherein, described polymerization toner further comprises and is selected from the group that comprises wax, chain-transferring agent, initiating agent, crosslinking chemical, lubricant and coupling agent one or more.
11, polymerization toner according to claim 10, wherein, described wax is selected from the group that comprises paraffin, microcrystalline wax, ceresine, polyester wax, Tissuemat E and polypropylene wax.
12, polymerization toner according to claim 10, wherein, described chain-transferring agent is to be selected from the group that comprises uncle's lauryl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, phenixin and carbon tetrabromide one or more.
13, according to each described polymerization toner of claim 1～9, this polymerization toner comprises: contain the polymerization of the core particulate of pigment, pigment stabiliser, charge control agent and binder resin monomer and monomer, crosslinking chemical and polymerization initiator by being used to form shell and the shell that forms on the core microparticle surfaces.
14, polymerization toner according to claim 13, wherein, described shell is made up of two-layer.
15, polymerization toner according to claim 13, wherein, described monomer and the described binder resin monomer that is used to form shell is identical or different, and this monomer that is used to form shell is the monomer that is selected from styrene-based, based on the monomer of acrylate, based on the monomer of methacrylate with based on one or more monomers in the monomer of diene, based on the total amount of binder resin monomer, its amount is 0.01～50 weight portion.
16, a kind of method for preparing polymerization toner, this method are included in pigment, pigment stabiliser, charge control agent and the binder resin monomer defined in each of claim 1～12 in the aqueous dispersant and carry out the step of suspension polymerization with the preparation toner particle.
17, method according to claim 16, wherein, described spreading agent is one or more spreading agents that are selected from the group that comprises inorganic dispersant, water-soluble organic polymer spreading agent and anionic surfactant.
18, a kind of method for preparing polymerization toner, this method may further comprise the steps:
In aqueous dispersion solution, pigment, pigment stabiliser, charge control agent and the binder resin monomer of claim 1～12 defined in each carried out suspension polymerization, with preparation toner core particulate; And
Under the situation that described toner core particulate exists, the monomer that is used to form shell carries out suspension polymerization, to form by one or more layers shell of forming on the surface of this toner core particulate.
19, method according to claim 18, wherein, described spreading agent is one or more spreading agents that are selected from the group that comprises inorganic dispersant, water-soluble organic polymer spreading agent and anionic surfactant.
20, a kind of chargeability of polymerization toner and method of charge stability improved, in the process of this polymerization toner of preparation, it is 2 that this method is used weight-average molecular weight, 000～200,000 styrene-butadiene-styrene block copolymer is as pigment stabiliser, and to use weight-average molecular weight be that 2,000～200,000 the multipolymer that contains sulphonate-base is as charge control agent.
21, method according to claim 20, wherein, cinnamic amount is 10～90wt% in styrene-butadiene-styrene block copolymer.
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